Detergent composition



United States Patent 3,359,208 DETERGENT COMPOSITION Arno Calm, PearlRiver, and Thaddeus J. Kaniecki, Brooklyn, N.Y., assignors to LeverBrothers Company, New York, N.Y., a corporation of Maine No Drawing.Original application Feb. 11, 1965, Ser. No. 431,982, now Patent No.3,267,135, dated Aug. 16, 1966. Divided and this application June 23,1966, Ser. No. 559,706

8 Claims. (Cl. 252-137) ABSTRACT OF THE DISCLOSURE A group ofN-(Z-hydroxyalkyl)-N-rnethyltaurine-N- oxides is disclosed which haveparticular value as the active detergent component in heavy dutydetergent formulations. Synthesis procedure for preparing the compoundsis also disclosed.

This is a division of our copending application Ser. No. 431,982 filedFeb. 11, 1965, now Patent No. 3,267,- 135, which in turn was acontinuation-in-part of our copending application, Ser. No. 173,377, nowPatent No. 3,171,787.

This invention relates to detergent compositions containingN-(Z-hydroxyalkyl)-N-methyltaurine-N-oxides or alkali metal saltsthereof as active ingredients.

The compounds,

where R is an alkyl group having from 8 to 18 carbon atoms, and M isselected from the group consisting of hydrogen and alkali metals, havebeen discovered.

The novel N-(2-hydroxyalkyl)-N-methyltaurine-N-oxides are excellentsurface-active agents and show detergency characteristics both alone andin the presence of conventional builder salts, such as alkali metalsulfates, carbonates, silicates, phosphates, borates, and mixturesthereof. The presence of conventional detergent builders generallyimproves the detergency of the compositions. Additional components, suchas carboxymethylcellulose which improves the dirt suspending propertiesof the Washing solution, may be used. Also, other synthetic detergents,soaps, perfumes, abrasives, foam stabilizers, germicidal agents,coloring agents and the like, may be included in the detergentcompositions of this invention. Accordingly, they are useful in dishwashing detergents, non-soap bars, soap bars, bars containing mixturesof soaps and non-soaps, shampoos, and to other applications known tothose skilled in the art where surface active properties are desired.

As will be noted below, another significant advantage of the compoundsof this invention is that the compounds within the series having thebest detergent characteristics are those where R has a chain length of13 to 18 carbon atoms, and can thus be obtained from less expensive rawmaterials.

The N-(Z-hydroxyalkyl)-N-methyltaurine-N-oxides of this invention areprepared by the oxidation of the correspondingN-(Z-hydroxyalkyl)-N-methyltaurine, according to the following equation:

OH CH3 1 I ROHCHaIlICHzCHzSOaM 1120 R and M having the same meaning asgiven above. While hydrogen peroxide is the preferred oxidizing agent,others, such as ozone, which have been described in the literature forthe conversion of amines to amine oxide may be used.

The N-(2hydroxyalkyl)-N-methyltaurine may be prepared with ease fromstarting materials which are relatively inexpensive and commerciallyavailable. A desirable method of preparing these compounds is by thesimple addition of N-methyltaurine to a long chain 1,2-epoxyalkane. Thissimple addition technique produces the desiredN-(Z-hydroxyalkyl)-N-methyltaurine, and the reaction product is freefrom inorganic salts which are difficult to remove. The preparation ofthe epoxide starting material may be by conventional methods such asoxidation of the compounds derived from petroleum sources.

The following examples describe the preparation and characteristics ofthe compounds of this invention, and

Example 1 A series of the novel compounds of this invention was preparedaccording to the following general procedure.

60 ml. of 30% hydrogen peroxide (0.536 mole) were slowly added to a warmalcoholic solution of sodium N-(Z-hydroxyalkyl)-N-methyltaurine,prepared by dissolving 0.134 mole of sodium N-(Z-hydroxyalkyD-N-methyltaurine in 350 ml. of 95% ethyl alcohol. The resultant solutionwas maintained at -50 C. for 24 hours. The excess hydrogen peroxide wasthen decomposed by placing a 1" x 2" piece of platinum foil into thesolution and allowing it to remain there for 2 to 4 days. When gasbubbles no longer formed on the surface of the platinum, it was removedfrom the reaction solution and the solvent was evaporated off. The lasttraces of solvent were removed by drying the residue at reducedpressure. The residue was finely powdered and suspended in 200 ml. ofacetone. The suspension was warmed to 40 C., filtered and the productair dried. Final drying was for 6 hours in a vacuum oven at 30 mm. and50 C. Table I lists the compounds prepared with this procedure.

Example 2 A series of N (Z-hydroxyalkyl)-N-methyltaurine-N- oxides wasprepared by the method of Example 1 and tested for detergency by theTerg-O-Tometer Detergency Test. This test gives an empirical measurementof the amount of soil removed from the fabric under simulated washingconditions. Sample swatches of cloth soiled in a standard manner with astandard soil are placed in a miniature washing machine, theTerg-O-Tometer apparatus, and laundered in the presence of a measuredamount of detergent and water of a standard hardness. A Terg-O- Tometerapparatus is described in the Journal of the American Oil ChemistsSociety, vol. 27, May 1950, pp.

153-159. After rinsing and drying, the reflectance of the cloths ismeasured and compared with the reflectance of the soiled cloths beforewashing.

In the detergency test referred to herein, the Terg-O- Tometer apparatuswas maintained in a water bath adjusted to maintain the temperature ofthe washing solution at 120 F. '2 F. The paddle oscillation was broughtto ninety complete cycles per minute and the paddle oscillated through a320 arc.

With the agitators in position on the machine, the detergent was addedin the desired amount to the washpot of the machine. 1250 ml. of waterhaving a hardness of 180 ppm. CaCO (60 parts magnesium and 120 partscalcium calculated as calcium carbonate) were added. The machine wasstarted and the solution agitated until the detergent was dissolved.

Cloth swatches approximately 4% inches by 6 inches were then added andwere washed for twenty minutes, after which the test swatches wereremoved from the solution and hand squeezed. The washpot was refilledwith clear rinse water of the same hardness used for washing at atemperature of 120 F. ;2 F., and, with the agitators running, the clothswere rinsed for minutes. The cloths were then removed, hand squeezed andironed dry. The reflectance of the cleaned cloths was measured with theHunter Reflectometer using the green filter.

The Terg-O-Tometer test was carried out in duplicate. The reflectancevalues in the table below represent the average of the actualreflectance readings taken from eight cloth swatches. Each of theN-(2-hydroxyalkyl)-N- methyltaurine-N-oxides was evaluated alone and inthe presence of tetrapotassium pyrophosphate, a conventional builder.Table II summarizes the results obtained.

TABLE II Terg-O-Tometer-Homologous series of sodium N-(2-hydroxyalkyl)-N-methyltaurine-N-oxides of formula:

Sodium N-(Z-hydroxyalkyl)-N-methyltaurine-N-0xides were prepared fromsodium N-(Z-hydroxyalkyl)-N-methyltaurines, which were in turn preparedby reacting N- methyltaurine with a 1,2-epoxyalkane mixture in which thealkane portion had, in one case, carbon chain lengths ranging from C toC and in the other case, from C to C The method of preparation describedin Example 1 was employed. These compounds were evaluated by theTerg-O-Tometer Test, both alone and in the presence of tetrapotassiumpyrophosphate. The mixed alkyl products showed slight detergency aloneand gave a good-toexcellent response to building. Table III below givesthe results of these evaluations.

4 TABLE 111 Terg-O-Torneter Tests of sodium N-(Z-hydroxyalkyD-N-methyltaurine-N-oxides of formula:

'Tetrapotasslum pyrophosphate.

Example 4 Three compounds of this invention were evaluated according tothe RAP Mildness Evaluation Test for Detergents. In this test, a 2%aqueous solution of the compound was tested on rabbit skin and theresults rated according to the following scale.

Mildness rating:

0No epidermal erosion (very mild) l-Foci or small patches of erosion(fair mildness) 225% to 50% destruction of epidermis (irritating)3-Greater than 50% epidermal erosion (very irritating) Table IV belowgives the compounds tested and the results of the test.

TABLE IV Compound Mildness Remarks Rating Sodium N(2-hydroxydodecyl)-ll- 0 Epidermis methyltaurine-N-oxide. normal. SodiumN-(2-hydroxytetradoeyD- 0 Do.

N-niethyltaurine-N-oxide. Sodium N-(2-hydroxyoctadecyl)- 0 Do.

N-methyltaurine-N-oxide.

The compounds of the present invention are also of exceptional utilityin the preparation of heavy-duty detergent formulations. Because suchformulations are commonly used in combination with hypochloritebleaches, it is important that they exhibit good sudsing and sudsstability in the presence of such bleaches.

Example 5 Using the above described formulation, test solutions Weremade by diluting the powdered detergent in water at a concentration of3.59 ozs./ 16 gals.

Test Cond tions Foam Volume, ml.

Vacuum N Bleach With Bleach 1 Water Foam Gleaner Hardness Booster DirtRF. 2 ES. 3 RF. F.S

0 Yes 90 40 100 40 sufficient sodium hypochlorite bleach was used toprovide 200 p.p.m. of available chlorine.

2 Foam formation, mins.

3 Foam stability, 5 mins.

4 The foam formation and stability was tested in the presence of 0.05%vacuum cleaner dirt.

5 Laurie isopropauolamide was added at a concentration correspondng to2.9% by weight of the basic test formulation.

The following are typical heavy-duty detergent formulations which may beused. These formulations, if tested as described in Example 5, Willyield similar improvements in foam formation and foam stability in thepresence of a hypochlorite bleach.

Percent N (2-hydroxyoctadecyl)-N-methyltaurine-N-oxide 10 Thenonylphenol-ethylene oxide adduct contains an average of 6 moles ofethylene oxide.

N-(Z-hydroxyalkyl)-N-methyltaurine-N-oxide 2 10 Sodium tripolyphosphate15 Tetrasodium pyrophosphate 35 Laurie isopropanolamide 3Carboxymethylcellulose 0.3 Water 10 Sodium sulfate 26.7

The alkyl group is a mixture of Clg-CQO alkyl groups.

N-(Z-hydroxydodecyl)-N-methyltaurine-N-oxide 5Linearalkylbenzenesulfonate (Na) 3 10 Coconut fatty acidmonoethanolamide 3 Tetrasodium pyrophosphate 35 Sodium tripolyphosphate15 Water 8 Sodium sulfate 24 3 The alkyl portion of the linearalkylbenzenesulfonate has an average of 12 carbon atoms.

Sodium C C alcohol-3-ethylene oxide sulfate 5 N (2hydroxytetradecyl)-N-methyltaurine-N- oxide 5 Tetrapotassiumpyrophosphate 40 Coconut fatty acid monoethanolamide 4 Laurieisopropanolamide 4 Sodium xylenesulfonate 3 Carboxymethylcellulose 0.3Water 10 Sodium sulfate 28.7

N (2 hydroxyoctadecyl) N-methyltaurine-N- Oxide 3 C -Calcohol-7.5-ethylene oxide 7 Coconut fatty acid monoethanolamide 5Carboxyrnethylcellulose 0.3 Sodium toluenesulfonate 8 Tetrapotassiumpyrophosphate 50 Water 26 Sodium sulfate 16.7

We claim: 1. A detergent composition consisting essentially of acompound of the formula wherein R is an alkyl group having from 8 to 18carbon atoms and M is selected from the group consisting of hydrogen andthe alkali metals in an amount suflicient to impart detergency to saidcomposition and an inorganic builder salt in an amount effective toimprove the detergency of said compound.

2. The detergent composition of claim 1, wherein the compound is aN-(Z-hydroxyhexadecyl) -N-methyltaurine- N-oxide.

3. The detergent composition of claim 1, wherein the compound is aN-(Z-hydroxyoctadecyl)-N-methyltaurine- N-oxide.

4. The detergent composition of claim 1, wherein the compound is thesodium salt of N-(2-hydroxyhexadecyl)- N-methyltaurine-N-oxide.

5. The detergent composition of claim 1, wherein the compound is thesodium salt of N-(Z-hydroxyoctadecyD- N-methyltaurine-N-oxide.

6. The detergent composition of claim 1, wherein R in the compound is amixture of alkyl groups, the carbon chains of which vary from C to C 7.The composition according to claim 1 wherein said builder is at leastone member of the group consisting of alkali metal sulfates, carbonates,silicates, phosphates, and borates and wherein said compound is presentin an amount of at least about 3% by Weight of said composition andwherein said builder is present in an amount of at least about 20% byweight of said composition.

8. A composition according to claim 7 wherein said builder is at leastone member of the group consisting of alkali metal tripolyphosphates andalkali metal pyrophosphates.

References Cited UNITED STATES PATENTS 1,944,300 1/1934 Ott et al260-513 2,658,072 11/1953 Kosmin 260-513 2,929,788 3/1960 Freese et al.252137 3,042,623 7/1962 Greene 252137 3,113,026 12/1963 Sprung 26050'1LEON D. ROSDOL, Primary Examiner. S. E. DARDEN, Assistant Examiner.

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A COMPOUND OF THEFORMULA